CN103031059A - Compositions and antireflective coatings for photolithography - Google Patents
Compositions and antireflective coatings for photolithography Download PDFInfo
- Publication number
- CN103031059A CN103031059A CN201210355169XA CN201210355169A CN103031059A CN 103031059 A CN103031059 A CN 103031059A CN 201210355169X A CN201210355169X A CN 201210355169XA CN 201210355169 A CN201210355169 A CN 201210355169A CN 103031059 A CN103031059 A CN 103031059A
- Authority
- CN
- China
- Prior art keywords
- composition
- compound
- alkyl
- corticosterone
- hydroxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 CCCOC*(C)N Chemical compound CCCOC*(C)N 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/111—Anti-reflection coatings using layers comprising organic materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
- G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Metallurgy (AREA)
- Materials For Photolithography (AREA)
- Silicon Polymers (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Paints Or Removers (AREA)
Abstract
Compositions for use in microelectronic applications: Ra comprises one or more multiple bonds, provided that, if Ra comprises more than one multiple bond, these multiple bonds are not in a conjugated configuration; and R1, R2, R3 are independently selected from alkoxyl, hydroxyl, halide, OC(O)R, OC(O)OR, wherein R is alkyl or a substituted alkyl; and Rb is selected from H or a saturated group comprising alkyl, alkylene, or alkylidene; and R4, R5, R6 are independently alkoxyl, hydroxyl, halide, OC(O)R, OC(O)OR, wherein R is alkyl or a substituted alkyl; and Rc comprises more than one multiple bond, and these multiple bonds are in a conjugated configuration; and R7, R8, R9 are independently alkoxyl, hydroxyl, halide, OC(O)R, OC(O)OR, wherein R is alkyl or a substituted alkyl; and R10, R11, R12, R13 are independently alkoxyl, hydroxyl, halide, OC(O)R, OC(O)OR, wherein R is alkyl or a substituted alkyl.
Description
The cross reference of related application
The application requires the right of priority of the U.S. Provisional Application 61/537,098 of submission on September 21st, 2011, and it incorporates the application into by reference.
Technical field
The present invention relates to the composition for microelectronic applications, particularly relate to the bottom anti-reflective coating (or " BARCs ") for microelectronic applications.In microelectronics industry, lasting needs have the microchip of pattern less and that more limit.The problem that now these development face comprises deteriorated (this is because the reflection on the interface of photo-resist layer and substrate causes) of the photo-resist profile of formation, and the thin resist layer that needs to adapt to shorter exposure wavelength and have enough elching resistants.Anti-reflection coating can be used for overcoming the above problems.A kind of method of making anti-reflection coating is by chemical vapour deposition (CVD), and this is expensive method.The expensive vacuum coat that needs to simplify photolithography (lithography) technique and avoid using anti-reflection layer.Therefore, need the composition of anti-reflection coating, this coating has high etch-selectivity about against corrosion, and can form by spin-coating method.
Background technology
The U.S. discloses 2009/0148789 and discloses siliceous organic coating composition, particularly anti-reflection coating composition, and said composition comprises the chromophoric group part, phenyl for example, and this group and Si atom separate.The disclosure also discloses siliceous foundation composition, and said composition is as liquid (organic solvent) composition preparation, and wherein at least a solvent in the solvent composition comprises hydroxyl.
The U.S. discloses 2007/0185298 and discloses curable organic silicic acid ester composition, uses it to form one or more layers of making electronic installation.Said composition comprises following: (a) have alkoxyl group or the acyloxy silane of at least one group, described group comprises the ethylenic degree of unsaturation and is bonded in Siliciumatom; (b) have alkoxyl group or the acyloxy silane of at least one group, this group comprises aromatic ring and is bonded in Siliciumatom; (c) latent acid catalyst; (d) at least one is bonded in optional alkoxyl group or the acyloxy silane of the C1-C6 alkyl of Siliciumatom.
United States Patent (USP) 5,621,034 discloses the composition of stable storing, comprises following: (A) have the hydroxyl that is bonded in Siliciumatom and/or the organopolysiloxane resins of alkoxyl group; (B) stablizer is selected from following: (B1) have the aliphatic polycarboxylic acid of at least two carboxyls, and (B2) have the aliphatic polycarboxylic acid's of at least two carboxyls carboxylic acid anhydride.
International open WO2009/088600 discloses the silsesquioxane resin that is used for anti-reflection coating, and wherein silsesquioxane resin has following formula: (PhSiO (
3-x)/2(OR ')
x)
m(HSiO (
3-x)/2(OR ')
x)
n(MeSiO (
3-x)/2(OR ')
x)
o(RSiO (
3-x)/2(OR ')
X)
p(R
2SiO (
3-x)/2OR ')
x)
qIn the formula, Ph is phenyl; Me is methyl; R is selected from the organo-functional group of sulfur-bearing; R ' is hydrogen atom or the hydrocarbyl group with 1 to 4 carbon atom; R
2Be selected from ester group, polyether group; With the polyethylene oxide group; The value of x is 0,1 or 2; The value of m is 0.01 to 0.97; The value of n is 0.01 to 0.97; The value of o is that 0.01 to 0.97:p value is 0.01 to 0.97; The value of q is 0 to 0.96; M+n+o+p+q ≈ l.
United States Patent (USP) 7,417,104 disclose the composition of the formation porous-film that comprises following component: (A) by having formula (1): R
1 n-Si-R
2 4-nThe polymkeric substance that obtains of the hydrolytic condensation of hydrolyzable silane.In the formula, R
1Unit price organic group or hydrogen, R
2Hydrolysable group or hydroxyl (n is integer 0 to 3), its hydrolysate or its part condensation product, condition is that at least a silicon compound has as R
1Organic crosslinkable groups.
The U.S. discloses 2010/0086872 " composition of the formation film of thermoset containing metal oxide " that discloses the film that is used to form containing metal oxide, and this film is forming being used for photolithographic multilayer resist method." composition of the formation film of thermoset containing metal oxide " comprises following at least component: (A) compound of containing metal oxide, by the hydrolysis-condensation reaction acquisition of hydrolyzable silicon compound and hydrolyzable metallic compounds; (B) heat cross-linking accelerator; (C) have unit price, divalence or the senior organic acid of 1 to 30 carbon atom; (D) trivalent or higher alcohols; (E) organic solvent.
United States Patent (USP) 6,268,457 disclose the anti-reflection coating material that is used for degree of depth UV-light etching method (photolithography), and it comprises one or more organic dye that are incorporated on glass knotting (spin-on-glass) material.Near suitable dyestuff wavelength region strong absorption light of 248nm and 193nm for example less than the wavelength of 260nm, this can be used for photoetch method.The method of the material of knotting on glass of preparation dyeing is included in the process of the material of knotting on the synthetic glass one or more organic dye is combined with the organoalkoxysilane reactant.
The U.S. discloses 2005/0277058 and discloses the composition that forms antireflection film, the polymkeric substance that it comprises organic solvent, linking agent and comprises the photoabsorption group, this polymkeric substance is by obtaining silicon compound, crosslinked group and the hydrolysis of non-crosslinked group and condensation more than one type.
The U.S. discloses 2010/0210765 and discloses the composition that forms the resist underlying membrane.The composition that forms the resist underlying membrane comprises following component: the polymkeric substance that has Siliciumatom in main chain; Compound with polynuclear plane; And organic solvent.Compound with polynuclear plane has at least two carboxyls as substituting group; These two carboxyls are bonded in two carbon atoms located adjacent one another individually, form polynuclear plane; Two carboxyls all have endo-configuration or exoconfiguration, or have cis-configuration.The polymkeric substance that has Siliciumatom in main chain can be formed by the mixture of organoalkoxysilane.
The other composition of antireflection film and/or other electronic application is disclosed in below with reference to document: United States Patent (USP) 7303785,7736837,5100503; The U.S. discloses 2005/0031964, and 2009/0148789.
But, the conventional siliceous BARC composition in this area for little critical size pattern (＜100nm) lack suitable optical property and lithography performance.And some conventional compositions comprise expensive and/or unsettled component.For example, some compositions comprises " containing Si-H's " compound, and this can and can react with the compound (such as alcohol and water) of hydroxyl with free radical usually.Some compositions includes organic dye, and this can increase the cost relevant with making such composition.Some compositions comprises expensive POSS (polyhedral oligomeric silsesquioxane ((RSiO1.5) 8).Some compositions comprises silsesquioxane/epoxy alkane, and this may cause pattern defect, for example scum silica frost (scum).
Therefore, still need the composition as the anti-reflection layer composition, said composition can be used to form photoengraving pattern less and that comparatively limit.Such composition that further need to have about the etching resist layer high etch-selectivity.Further need to use spin-coating method to form the cost-efficient composition of anti-reflection layer.These need and other needs to be satisfied by following the present invention.
Summary of the invention
The invention provides the first composition that comprises following at least component:
A) be selected from the compound F 17-hydroxy-corticosterone 1 of formula 1:
Wherein Ra comprises one or more multiple bonds (that is, two keys or triple bond), comprises C=C, C ≡ C, C=O, C=N and C ≡ N, and condition is, if Ra comprise more than a multiple bond, these multiple bonds are not the configuration of conjugation so; Be selected from independently of one another alkoxyl group, hydroxyl, halogen, OC (O) R or OC (O) OR with R1, R2 and R3, wherein R is the alkyl of alkyl or replacement; With
B) be selected from the compound F 17-hydroxy-corticosterone 2 of formula 2
(formula 2),
Wherein Rb is selected from H or saturated group, and described saturated group comprises alkyl, alkylene or alkylidene; R4, R5 and R6 are selected from alkoxyl group, hydroxyl, halogen, OC (O) R or OC (O) OR independently of one another, and wherein R is the alkyl of alkyl or replacement; With
C) be selected from the compound F 17-hydroxy-corticosterone 3 of formula 3:
Wherein Rc comprises more than a multiple bond, comprise C=C, C ≡ C, C=O, C=N and C ≡ N, and these multiple bonds is the configuration of conjugation; R7, R8 and R9 are selected from alkoxyl group, hydroxyl, halogen, OC (O) R or OC (O) OR independently of one another, and wherein R is the alkyl of alkyl or replacement; With
D) be selected from the compound F 17-hydroxy-corticosterone 4 of formula 4:
Wherein R10, R11, R12 and R13 are selected from alkoxyl group, hydroxyl, halogen, OC (O) R or OC (O) OR independently of one another, and wherein R is the alkyl of alkyl or replacement.
Description of drawings
Fig. 1 has described the schematic diagram of the trilamellar membrane structure on the silicon wafer.
Fig. 2 is the cross-sectional view of the straight-line pattern of generation after photolithography, below the explanation: (a) perfect square pattern; (b) has the defective pattern of scum silica frost.
Fig. 3 has described " top-down " SEM image of wafer surface after photolithography, illustrates that complete pattern destroys (complete pattern collapse).
Fig. 4 is wafer surface " top-down " SEM image after photolithography, and pattern breaking limit (Pattern Collapse Margin) is described.
Fig. 5 is the SEM image (embodiment 16,42nm groove/84nm pitch (pitch)) with photolithography pattern of scum silica frost.
Fig. 6 is the SEM image (Comparative Examples G, 42nm groove/84nm pitch) with photolithography pattern of scum silica frost.
Embodiment
As above discuss, the invention provides the first composition that comprises following at least component:
A) be selected from the compound F 17-hydroxy-corticosterone 1 of formula 1:
(formula 1),
Wherein Ra comprises one or more multiple bonds, comprises C=C, C ≡ C, C=O, C=N and C ≡ N, and condition is, if Ra comprise more than a multiple bond, these multiple bonds are not the configuration of conjugation so; With
R1, R2 and R3 are selected from alkoxyl group, hydroxyl, halogen, OC (O) R or OC (O) OR independently of one another, and wherein R is the alkyl of alkyl or replacement; With
B) be selected from the compound F 17-hydroxy-corticosterone 2 of formula 2
Wherein Rb is selected from H or saturated group, and described saturated group comprises alkyl, alkylene or alkylidene; With
R4, R5 and R6 are selected from alkoxyl group, hydroxyl, halogen, OC (O) R or OC (O) OR independently of one another, and wherein R is the alkyl of alkyl or replacement; With
C) be selected from the compound F 17-hydroxy-corticosterone 3 of formula 3:
(formula 3),
Wherein Rc comprises more than a multiple bond, comprise C=C, C ≡ C, C=O, C=N and C ≡ N, and these multiple bonds is the configuration of conjugation; With
R7, R8 and R9 are selected from alkoxyl group, hydroxyl, halogen, OC (O) R or OC (O) OR independently of one another, and wherein R is the alkyl of alkyl or replacement; With
D) be selected from the compound F 17-hydroxy-corticosterone 4 of formula 4:
Wherein R10, R11, R12 and R13 are selected from alkoxyl group, hydroxyl, halogen, OC (O) R or OC (O) OR independently of one another, and wherein R is the alkyl of alkyl or replacement.
In one embodiment, the first composition comprises the Si more than or equal to 5wt%, or more than or equal to the Si of 10wt%, or more than or equal to the Si of 15wt%, based on the gross weight of compound F 17-hydroxy-corticosterone 1, F2, F3 and F4.
In one embodiment, the integral molar quantity of compound F 17-hydroxy-corticosterone 2 and compound F 17-hydroxy-corticosterone 4 is more than or equal to 40 % by mole, based on the total mole number of compound F 17-hydroxy-corticosterone 1, F2, F3 and F4.
In one embodiment, the integral molar quantity of compound F 17-hydroxy-corticosterone 2 and compound F 17-hydroxy-corticosterone 4 is less than or equal to 85 % by mole, or is less than or equal to 80 % by mole, based on the total mole number of compound F 17-hydroxy-corticosterone 1, F2, F3 and F4.
In one embodiment, the amount of compound F 17-hydroxy-corticosterone 4 is greater than 10 % by mole, based on the total mole number of compound F 17-hydroxy-corticosterone 1, F2, F3 and F4.
In one embodiment, the mol ratio of F1/F4 is 1/20 to 1/1, or is 1/15 to 1/1, or is 1/10 to 1/1.
In one embodiment, for the first composition, F1 is 5 to 50wt%, or is 10 to 30wt%; F2 is 5 to 50wt%, or is 10 to 40wt%; F3 is 2 to 20wt%, or is 2 to 10wt%; F4 is 20 to 80wt%, or is 30 to 80wt%.Each weight percent is all based on the weight of the first composition.
In one embodiment, for the first composition, the amount of compound F 17-hydroxy-corticosterone 1 is 10 to 90 % by mole, further is 15 to 90 % by mole, further is 20 to 90 % by mole, further is 25 to 90 % by mole, based on the total mole number of compound F 17-hydroxy-corticosterone 1, F2, F3 and F4.
In one embodiment, for the first composition, the amount of compound F 17-hydroxy-corticosterone 1 is greater than 10 % by mole, further greater than 12 % by mole, based on the total mole number of compound F 17-hydroxy-corticosterone 1, F2, F3 and F4.
In one embodiment, for the first composition, the amount of compound F 17-hydroxy-corticosterone 4 is 10 to 65 % by mole, further is 10 to 60 % by mole, further is 10 to 55 % by mole, further is 10 to 50 % by mole, based on the total mole number of compound F 17-hydroxy-corticosterone 1, F2, F3 and F4.
In one embodiment, for the first composition, the amount of compound F 17-hydroxy-corticosterone 4 is less than 65 % by mole, further less than 60 % by mole, based on the total mole number of compound F 17-hydroxy-corticosterone 1, F2, F3 and F4.
The first composition can comprise the combination of the embodiment that two or more the application describe.
The present invention also provides the prepolymer that is formed by the first composition.In further embodiment, prepolymer forms by following steps at least: make the hydrolysis of the first composition form the product that is hydrolyzed, and make the product condensation of hydrolysis.
In one embodiment, the Mw of prepolymer is 1,000 to 20,000 g/mol, or is 1,000 to 10,000 g/mol, or is 1,000 to 5,000 g/mol, determines by conventional GPC.
In one embodiment, the Mw/Mn of prepolymer is 1.1 to 6, or is 1.2 to 5, or is 1.5 to 4.
Prepolymer of the present invention can comprise the combination of the embodiment that two or more the application describe.
The present invention also provides the second composition, and described the second composition comprises prepolymer of the present invention; At least a with in the following material: contain the compound of amine, halogen-containing compound, hydrochloride contains the compound of ammonium or its mixture.
The second composition can comprise the combination of the embodiment that two or more the application describe.
The present invention also provides the crosslinked composition that is formed by the second composition.
The present invention also provides the goods that comprise at least one parts that formed by the present composition.
The present invention also provides the goods that comprise at least one parts that formed by the first composition.
The present invention also provides the goods that comprise at least one parts that formed by the second composition.
The present invention also provides the goods that comprise at least one parts that formed by prepolymer of the present invention.
In one embodiment, goods are films.
The present invention also provide comprise at least one by the present composition form the layer film.In further embodiment, film comprises at least two layers.In further embodiment, the second layer is formed by the 3rd composition that comprises at least a polymkeric substance.
The present invention also provides the film that comprises at least two layers, and wherein at least one layer is the anti-reflection layer that is formed by the present composition, and the described present composition is the first composition or the second composition for example.In further embodiment, other layer is the photo-resist layer.
The present invention also provides the film that comprises at least two layers, and wherein at least one layer is the anti-reflection layer that is formed by the first composition.In further embodiment, another layer is the photo-resist layer.
The present invention also provides the film that comprises at least two layers, and wherein at least one layer is the anti-reflection layer that is formed by the second composition.In further embodiment, another layer is the photo-resist layer.
Goods of the present invention can comprise the combination of the embodiment that two or more the application describe.
Film of the present invention can comprise the combination of the embodiment that two or more the application describe.
The present invention also is provided at the method that forms coating in the substrate, and described method comprises at least following steps:
Substrate is provided;
Form bottom in described substrate, wherein said bottom comprises at least a polymkeric substance;
The present invention's the first composition or the present invention's the second composition are applied on the described bottom, and
Make the first composition or the second composition solidify to form described coating.
In further embodiment, the method comprises that at least a composition that will comprise at least a photo-resist polymkeric substance is applied on the coating.
In one embodiment, a plurality of layers with the first composition or the second composition are applied on the bottom.
In one embodiment, coating is anti-reflection layer.
The present invention also is provided at the method that forms coating in the substrate, and described method comprises at least following steps:
Substrate is provided;
The present invention's the first composition or the present invention's the second composition are applied at least a portion of substrate, or are applied in one or more being applied on the described suprabasil middle layer; With
Make the first composition or the second composition solidify to form coating.
In further embodiment, the method comprises that at least a composition that will comprise at least a photo-resist polymkeric substance is applied on the coating.
In one embodiment, a plurality of layer of the first composition or the second composition is applied at least a portion of substrate, or is applied in one or more being applied on the described suprabasil middle layer.
In one embodiment, coating is anti-reflection layer.
Method of the present invention can comprise the combination of the embodiment that two or more the application describe.
Compound F 17-hydroxy-corticosterone 1-F4
The following description of compound F 17-hydroxy-corticosterone 1, F2, F3 and F4.
A) be selected from the compound F 17-hydroxy-corticosterone 1 of formula 1:
Wherein Ra comprises one or more multiple bonds, comprises C=C, C ≡ C, C=O, C=N and C ≡ N, and condition is that if Ra comprises more than a multiple bond, these multiple bonds are not the configuration of conjugation so; R1, R2 and R3 are selected from alkoxyl group, hydroxyl, halogen, OC (O) R or OC (O) OR independently of one another, and wherein R is the alkyl of alkyl or replacement.In further embodiment, R is alkyl.
In one embodiment, Ra comprises one or more in alkenyl, alkynyl, imide, itrile group, ketone group, ester group, amide group or the carbonate group, and it comprises 2 to 10 carbon atoms; R1, R2 and R3 are selected from OH, OR or OC (O) R independently of one another, and wherein R is C
1-C
10Alkyl or C
1-C
10The alkyl that replaces.
In one embodiment, Ra comprises one or more in alkenyl, alkynyl, imide, itrile group, ketone group, ester group, amide group or the carbonate group, and it comprises 2 to 10 carbon atoms; R1, R2 and R3 are selected from OH, OR or OC (O) R independently of one another, and wherein R is C
1-C
10Alkyl.
In one embodiment, Ra is selected from vinyl, allyl group, propenyl, butenyl, acetoxyl group, cyano ethyl, acetyl ethyl or kharophen propyl group; R1, R2 and the R3 OR that respectively does for oneself, wherein R is selected from methyl independently of one another, ethyl, n-propyl, 2-propyl group, normal-butyl, isobutyl-, or 2-butyl.
In one embodiment, compound F 17-hydroxy-corticosterone 1 is selected from vinyltrimethoxy silane or vinyltriethoxysilane.
B) be selected from the compound F 17-hydroxy-corticosterone 2 of formula 2:
Wherein Rb is selected from H or saturated group, and described saturated group comprises alkyl, alkylene or alkylidene; R4, R5 and R6 are selected from alkoxyl group, hydroxyl, halogen, OC (O) R or OC (O) OR independently of one another, and wherein R is the alkyl of alkyl or replacement.In further embodiment, R is alkyl.
In one embodiment, Rb is selected from saturated group, and it comprises alkyl, alkylene or alkylidene; R4, R5 and R6 are selected from alkoxyl group, hydroxyl, halogen, OC (O) R or OC (O) OR independently of one another, and wherein R is the alkyl of alkyl or replacement.In further embodiment, R is alkyl.
In one embodiment, Rb comprises following saturated group: replace or unsubstituted C
1-C
10Cyclic alkyl replaces or unsubstituted C
1-C
10Acyclic alkyl replaces or unsubstituted C
1-C
10The ring-type alkylene replaces or unsubstituted C
1-C
10Acyclic alkylene replaces or unsubstituted C
1-C
10The ring-type alkylidene replaces or unsubstituted C
1-C
10Acyclic alkylidene, or H; Or unsubstituted C
1-C
10Cyclic alkyl, unsubstituted C
1-C
10Acyclic alkyl, unsubstituted C
1-C
10The ring-type alkylene, unsubstituted C
1-C
10Acyclic alkylene, unsubstituted C
1-C
10The ring-type alkylidene, unsubstituted C
1-C
10Acyclic alkylidene, or H; Or unsubstituted C
1-C
10Cyclic alkyl, unsubstituted C
1-C
10Acyclic alkyl, or H; Or unsubstituted C
1-C
10Cyclic alkyl, or unsubstituted C
1-C
10Acyclic alkyl; Or unsubstituted C
1-C
10Acyclic alkyl; Be selected from independently of one another OH with R4, R5 and R6, OR, or OC (O) R, wherein R is C
1-C
10Alkyl or C
1-C
10The alkyl that replaces.In further embodiment, R is C
1-C
10Alkyl.
In one embodiment, Rb is selected from methyl, ethyl, n-propyl, 2-propyl group, normal-butyl, isobutyl-, or 2-butyl; R4, R5 and the R6 OR that respectively does for oneself, wherein R is selected from methyl independently of one another, ethyl, n-propyl, 2-propyl group, normal-butyl, isobutyl-, or 2-butyl.
In one embodiment, compound F 17-hydroxy-corticosterone 2 is selected from methyltrimethoxy silane or Union carbide A-162.
C) be selected from the compound F 17-hydroxy-corticosterone 3 of formula 3:
Wherein Rc comprises more than a multiple bond, comprise C=C, C ≡ C, C=O, C=N and C ≡ N, and these multiple bonds is the configuration of conjugation; R7, R8 and R9 are selected from alkoxyl group, hydroxyl, halogen, OC (O) R or OC (O) OR independently of one another, and wherein R is the alkyl of alkyl or replacement.In further embodiment, R is alkyl.
In one embodiment, Rc comprises the aryl of aryl or replacement, conjugated diolefine or conjugated triene, the conjugation diketone, conjugation ketone ester, α, beta-unsaturated esters, alpha, beta-unsaturated ketone, nitrile with the alkene conjugation, with the nitrile of ketone conjugation, with the nitrile of ester conjugation, with the alkynes of alkene conjugation, with the alkynes of ketone conjugation, or with the alkynes of ester conjugation; Be selected from independently of one another OH, OR or OC (O) R with R7, R8 and R9, wherein R is C
1-C
10Alkyl or C
1-C
10The alkyl that replaces.In further embodiment, R is C
1-C
10Alkyl.
In one embodiment, Rc comprises phenyl, naphthyl, anthryl, phenanthryl, fluorenyl, pyridyl, quinolyl, imidazolyl, benzimidazolyl-, indyl, carbazyl, furyl, benzofuryl, dibenzofuran group, acryloxy, acrylamido, methacryloxy, or methacryloyl amido; With R7, R8 and the R9 OR that respectively does for oneself, wherein R is selected from methyl independently of one another, ethyl, n-propyl, 2-propyl group, normal-butyl, isobutyl-, or 2-butyl.
In one embodiment, compound F 17-hydroxy-corticosterone 3 is selected from phenyltrimethoxysila,e or phenyl triethoxysilane.
D) be selected from the compound F 17-hydroxy-corticosterone 4 of formula 4:
Wherein R10, R11, R12 and R13 are selected from alkoxyl group, hydroxyl, halogen, OC (O) R or OC (O) OR independently of one another, and wherein R is the alkyl of alkyl or replacement.In further embodiment, R is alkyl.
In one embodiment, R10, R11, R12 and R13 are selected from OH, OR or OC (O) R independently of one another, and wherein R is C
1-C
10Alkyl or C
1-C
10The alkyl that replaces.In further embodiment, R is C
1-C
10Alkyl.
In one embodiment, R10, R11, R12 and R13 are OR, and wherein R is selected from methyl independently of one another, ethyl, n-propyl, 2-propyl group, normal-butyl, isobutyl-, or 2-butyl.
In one embodiment, compound F 17-hydroxy-corticosterone 4 is selected from positive quanmethyl silicate or tetraethyl orthosilicate:
Three layers of coating
Three layers of coating, for example, three layers of resist layer generally include: (a) at suprabasil curable foundation composition; (b) be applied in hard mask (hardmask) composition on the curable compositions (hard mask layer that the present composition of for example, being described by the application forms); (c) be applied in photo-corrosion-resisting agent composition layer on the hard mask compositions.Substrate suitably is any substrate for the method that relates to photo-resist.For example, substrate can be silicon, silicon-dioxide or aluminium-aluminum oxide microelectronic die.Also can use gallium arsenide, silicon carbide, pottery, quartz or copper substrate.Also can suitably use the substrate for liquid-crystal display or other flat panel display applications, substrate of glass for example, the substrate of tin indium oxide coating etc.Also can use the substrate for optics and photoelectron device (for example waveguide).Coating composition and photolithography be described in the U.S. disclose 2007/0238052 and the U.S. disclose 2009/0148789, separately by with reference to incorporating the application into.
Multiple photo-resist can use together with coating composition combination of the present invention (that is, outer coating).Preferred photo-resist comprises the resist that chemistry strengthens, particularly positive interaction (positive-acting) or negative interaction (negative-acting) photo-resist, it comprises one or more actinic acids (photoacid) propellant compound and resin Composition, and the acid that this resin Composition is included in the light generation exists lower experience to take off the unit (for example unsettled ester of actinic acid, acetal, ketal or ether unit) of end-blocking (deblocking) or scission reaction.
The negative interaction photo-resist also can use with coating composition of the present invention, for example the resist of crosslinked after being exposed to activating radiation (that is, curing or sclerosis).The preferred photo-resist that uses together with coating composition of the present invention can be with relative short wavelength radiation imaging, and for example, wavelength is less than 300nm or less than 260nm, and for example approximately radiation of 248nm, or wavelength is less than approximately 200nm, for example radiation of 193nm.
Suitable photo-resist comprises actinic acid propellant compound and one or more resins of imaging significant quantity.Suitable resin includes but not limited to, i) comprises the resol (for example, referring to United States Patent (USP) 6,042,997 and 5,492,793) of acid-unstable group; Ii) comprise the polymkeric substance of the polymerized unit of following material: vinylphenol, do not comprise hydroxyl or carboxyl ring substituents optional replacement ethenylphenyl (for example, vinylbenzene), with alkyl acrylate for example about above polymer i) describe those take off capping group (deblocking group), for example be described in United States Patent (USP) 6,042,997 polymkeric substance; And iii) comprise with the repeating unit of the acetal of actinic acid reaction or ketal part and the optional aromatic repeating units polymkeric substance of phenyl or phenolic group group for example; Such polymkeric substance has been described in United States Patent (USP) 5,929, and 176 and 6,090,526.
Other resin comprises basically or do not contain phenyl or other aryl fully, and can provide and be specially adapted at the following wavelength of the 200nm resin of the chemical reinforced slushing compound of 193nm imaging for example.Such preferred resin comprises: i) comprises for example polymkeric substance of the polymerized unit of the optional norbornylene that replaces of non-aromatic cyclic olefin (the two keys of interior ring-type), for example is described in United States Patent (USP) 5,843, and 624 and 6,048,664 polymkeric substance; Ii) comprise the polymkeric substance of acrylic acid alkyl ester units, described alkyl acrylate is tert-butyl acrylate for example, Tert-butyl Methacrylate, vinylformic acid methyl adamantane base ester, the firm alkyl ester of methyl methacrylate fund, and other acyclic alkyl and alicyclic acrylate; Such polymkeric substance has been described in United States Patent (USP) 6,057,083; The disclosed application EP01008913A1 in Europe and EP00930542A1, and iii) comprises the maleic anhydride of acid anhydride unit, particularly polymerization of polymerization and/or the polymkeric substance of itaconic anhydride unit, as be disclosed in Europe disclosed application EP01008913A1 and United States Patent (USP) 6,048,662.
Other resin comprises and comprises the resin with heteroatomic repeating unit, and heteroatoms is oxygen and/or sulphur (but be different from acid anhydride, namely this unit does not comprise the carbonyl annular atoms) particularly, and preferably is substantially free of or do not contain any aromatic units fully.Preferably, assorted alicyclic ring element condenses in resin backbone, and further preferably wherein resin comprise the alicyclic ring element of the carbon that condenses (for example the polymerization by the norbornylene group provides) and/or acid anhydride unit (for example the polymerization by maleic anhydride or itaconic anhydride provides).Equally, comprise the resin (fluoropolymer) of fluoro substituents, for example, can be provided by the polyreaction of tetrafluoroethylene, aryl such as fluorophenethyl ene compound of fluoridizing etc.
Definition
Term used in this application " composition " comprises the mixture of the material that consists of composition and reaction product and the degradation production that is formed by the material of composition.
Term used in this application " polymkeric substance " refers to the macromolecular compound by the monomer polymerization preparation that makes identical or different type.Therefore general term polymer comprises term homopolymer (only being used for representing that the impurity that wherein should understand trace can be entrained in the polymer architecture by the polymkeric substance of one type monomer preparation), and as the term interpretation that hereinafter limits.
Term used in this application " interpretation " refers to the polymkeric substance by the polyreaction preparation of at least two kinds of dissimilar monomers.General term interpretation comprises multipolymer (be used for represent by two kinds of different monomers preparations polymkeric substance), and by the polymkeric substance more than two kinds of dissimilar monomers preparations.
Term used in this application " prepolymer " refers to molecular weight Mw (weight average), for example be approximately 500 g/mols to 100,000, g/mole, be preferably 500 to 50,000 g/mols and (determined polymkeric substance as described below) by conventional GPC.
Term used in this application " multiple bond " can represent two keys or triple bond.
Term used in this application " conjugation configuration " refers to appear at the configuration of the multiple bond in the compound, wherein two multiple bonds by a singly-bound separately, form alternate mode (for example, " the two keys of Shuan Jian – Dan Jian – " or " the two keys of San Jian – Dan Jian – " or " Shuan Jian – Dan Jian – triple bond ").In the configuration of conjugation, multiple bond can be two keys or triple bond independently.May reside in more than an alternate mode in the compound of the conjugation configuration with key.Example with compound of conjugated link(age) is benzene, Isosorbide-5-Nitrae-divinyl, furans, vinyl cyanide, and vinylformic acid.
Benzene Isosorbide-5-Nitrae-divinyl furanacrylonitrile vinylformic acid
Term used in this application " compound that contains amine " refers to comprise at least one, be preferably an amine groups (for example, primary amine, secondary amine or tertiary amine (NH
2Or NH or N)) organic compound.
Term used in this application " halogen-containing compound " refers to comprise at least one, is preferably a halogen group organic compound of (for example, Cl, Br, F, be preferably Cl).
The existence that term " comprises ", any other component, step or process do not got rid of in " comprising ", " having " and their derivative, and no matter whether the application disclosed them especially.For eliminating any query, unless opposite explanation, all the application are by using term " to comprise " that claimed composition can comprise any additional additive, auxiliary material or compound (regardless of whether as polymerization).On the contrary, except for unnecessary those of processing property, term " basically by ... form " will any other component, step or process get rid of outside the how lower scope of narrating in office.Term " by ... form " do not comprise component, step or the process not describing especially or list.
Testing method
GPC
The molecular weight of prepolymer is also referred to as size exclusion chromatography (SEC) monitoring by gel permeation chromatography (GPC).These instrument and equipment have one group of post, these posts be applicable to useful range be approximately 500 g/mols at least about 100,000 g/mols molecular weight, styrene-based calibration sample.Special effectively one group of two SHODEX LF-804GPC post installing with series system, 8mm diameter x300mm length is available from Thomson Instrument Co..Moving phase is tetrahydrofuran (THF), and with the speed pumping of 1mL/min.This instrument also is equipped with RI-detector.Calibration uses polystyrene standards to carry out, and this standard specimen is available from Polymer Standards Service GmbH, Mainz, Germany.Mn, Mw and MWD use " GPC-addon " of ChemStation software to calculate, available from Agilent Technologies, Inc..
SEM
Top-down and cross sectional image is all measured at Hitachi CG 4000SEM (Hitachi High Technologies America, Inc).Top-down measurement is carried out at the wafer of whole imaging.Cross section is by shearing wafer, also using the thin layer sputter coated wafer piece of gold or iridium to obtain through useful feature.
Experiment
Being used for material of the present invention uses available from commercial source and former state.Abbreviation and the source of raw material are:
VTMS: vinyltrimethoxy silane (Sigma Aldrich, Dow Corning)
MTMS: methyltrimethoxy silane (Sigma Aldrich, Dow Corning)
PTMS: phenyltrimethoxysila,e (Sigma Aldrich, Dow Corning)
TEOS: tetraethyl orthosilicate (Sigma Aldrich, Dow Corning)
GlyTMS: glycidoxypropyltrimewasxysilane (Glycidoxypropyltrimethoxysilane) (Sigma Aldrich, Dow Corning, Gelest)
PGMEA: propylene glycol methyl ether acetate (DOWANOL PMA, The Dow Chemical Company)
BTEAC: benzyltriethylammoinium chloride (Sigma Aldrich)
The 3N acetic acid aqueous solution prepares in the laboratory.Glacial acetic acid is provided by JT Baker.
0.1N aqueous hydrochloric acid prepares in the laboratory.Concentrated hydrochloric acid is provided by Fisher.
Table 1 has been listed and has been used for different the first compositions of the present invention.Content in mol%, based on the sum that adds with the mole number of preparation composition.
The description of table 1. the first composition
Different prepolymers uses above composition synthetic as shown in table 2A and 2B.Describe in the paragraph of the detailed building-up process of prepolymer after table 2B.
Table 2A: the description of prepolymer
Table 2B: the description of prepolymer is continuous
Synthesizing of prepolymer of the present invention and contrast prepolymer
Prepolymer 1
The water (20.52mL) that the submicron of glacial acetic acid (0.52mL) and the HPLC grade of packing in being equipped with three neck round-bottomed flasks of mechanical stirrer and short-path distillation equipment is filtered is to form acetic acid/water solution.Phenyltrimethoxysila,e (6.16g packs in the plastic injector that is equipped with transfer lines (transfer line), 31.1mmol), methyltrimethoxy silane (21.64g, 158.8mmol), vinyltrimethoxy silane (7.68g, 51.8mmol), the premixed solution of tetraethyl orthosilicate (21.58g, 103.6mmol) and PGMEA (58.33mL).Use syringe pump during 1 hour in, organoalkoxysilane monomer/PGMEA mixture is dropwise added in the acetic acid/water solution.After adding, the syringe transfer lines is removed from the round-bottomed flask entrance, and substitute with the monitoring internal reaction temperature with the thermopair of equipping adapter glass.Reaction mixture was stirring at room 10 minutes.Then flask is put in the oil bath of controlled temperature, oil bath temperature is set to the temperature that reaches 100 ° of C.Condensation reaction is carried out under nitrogen atmosphere, collects alcohol and water by distillation simultaneously.With reaction mixture heating 2 hours 25 minutes.Then use PGMEA (42mL) that dense reaction mixture is diluted to approximately 20wt% solid, reach the final weight of 127.4g.Solution filters through 0.2 μ m PTFE membrane filter.
Solids concn is by dry 1g sample determination in the baking oven of 110 ° of C.Molecular weight is determined by GPC: Mw, 4152 g/mols; Mn, 1414 g/mols; MWD, 2.94.
Prepolymer 2
Phenyltrimethoxysila,e (6.16g packs in being equipped with three neck round-bottomed flasks of mechanical stirrer and short-path distillation equipment, 31.1mmol), methyltrimethoxy silane (21.64g, 158.8mmol), vinyltrimethoxy silane (7.68g, 51.8mmol), the premixed solution of tetraethyl orthosilicate (21.58g, 103.6mmol) and PGMEA (58.33mL).The water (27.98mL) that the submicron of glacial acetic acid (0.52mL) and the HPLC grade of packing in being equipped with the plastic injector of transfer lines is filtered.During 30 minutes, use syringe pump that acetic acid/water solution is added in organoalkoxysilane monomer/PGMEA mixture.After adding, the syringe transfer lines is removed from the round-bottomed flask entrance, and substitute with the monitoring internal reaction temperature with the thermopair of equipping adapter glass.Flask is put in the oil bath of controlled temperature, oil bath temperature is set to the temperature that reaches 100 ° of C.Condensation reaction is carried out under nitrogen atmosphere, collects alcohol and water by distillation simultaneously.Reaction mixture is heated two and one-half-hours.Then use PGMEA (42mL) that dense reaction mixture is diluted to approximately 20wt% solid, reach the final weight of 127g.Solution filters through 0.2 μ mPTFE membrane filter.Solids concn is by dry 1g sample determination in the baking oven of 110 ° of C.Molecular weight is determined by GPC: Mw, 4627 g/mols; Mn, 1709 g/mols; PDI, 2.71.
Prepolymer 3
The 3N acetic acid (34.21g) of in the 250-mL three neck round-bottomed flasks that are equipped with magnetic stirring apparatus and short-path distillation equipment, packing into.The premixed solution of the phenyltrimethoxysila,e of in being equipped with the plastic injector of transfer lines, packing into (8.82g), methyltrimethoxy silane (17.49g), vinyltrimethoxy silane (10.96g), tetraethyl orthosilicate (51.36g) and PGMEA (82mL).Use syringe pump that monomer solution is slowly added in the reaction flask.After adding 1 hour that monomer begins, flask is put in the oil bath of controlled temperature, oil bath temperature is set to 100 ° of C.After 3 hours, make oil bath temperature increase to 110 ° of C, and remain on this temperature, until the temperature in the reaction mixture reaches 90 ° of C.Then remove oil bath, and make the polymers soln cooling.Add the PGMEA of the second equal portions, thereby polymers soln is adjusted to the 20wt% solid.The solid content of polymers soln was determined by the sample of heated polymerizable thing solution in the baking oven of 145 ° of C in 1 hour.The molecular weight of polymkeric substance is determined by GPC: 3083 g/mols of Mw; 1396 g/mols of Mn; MWD 2.21.
Prepolymer 4
In being equipped with the 500-mL three neck round-bottomed flasks of magnetic stirring apparatus and Dean Stark equipment, pack into glacial acetic acid (13.33g) and water (59.98g).The premixed solution of the phenyltrimethoxysila,e of in being equipped with the plastic injector of transfer lines, packing into (18.86g), methyltrimethoxy silane (37.41g), vinyltrimethoxy silane (23.48g), tetraethyl orthosilicate (110.04g) and PGMEA (175.07g).Use syringe pump monomer solution to be added in the reaction flask in during 1 hour.Flask is put into the oil bath of the controlled temperature that is set in 100 ° of C, and kept 1 hour in this temperature.Begin to collect distillment.Make oil bath temperature increase to 110 ° of C, and remain on this temperature, until temperature of reaction reaches 90 ° of C, remove heating bath at this point, make the polymers soln cooling.Add the PGMEA of the second equal portions, thereby polymers soln is adjusted to the 20wt% solid.The solid content of polymers soln was determined by the sample of heated polymerizable thing solution in the baking oven of 145 ° of C in 1 hour.The molecular weight of polymkeric substance is determined by GPC: 2443 g/mols of Mw; 1419 g/mols of Mn; MWD 1.72.
The 3N acetic acid (34.5g) of in the 250-mL three neck round-bottomed flasks that are equipped with mechanical stirrer and short-path distillation equipment, packing into.The premixed solution of the phenyltrimethoxysila,e of in being equipped with the plastic injector of transfer lines, packing into (8.81g), methyltrimethoxy silane (17.46g), vinyltrimethoxy silane (10.95g), tetraethyl orthosilicate (51.36g) and PGMEA (82mL).Use syringe pump that monomer solution is slowly added in the reaction flask.After adding 1 hour that monomer begins, the oil bath of flask being put into controlled temperature, and oil bath temperature is set in 100 ° of C.After 3 hours, oil bath temperature increases to 110 ° of C, and remains on this temperature, until temperature of reaction reaches 90 ° of C, removes oil bath at this point, makes the polymers soln cooling.Add the PGMEA of the second equal portions, thereby polymers soln is adjusted to the 20wt% solid.The solid content of polymers soln was determined by the sample of heated polymerizable thing solution in the baking oven of 145 ° of C in 1 hour.The molecular weight of polymkeric substance is determined by GPC: 2928 g/mols of Mw.
Vinyltrimethoxy silane (11.1g), phenyltrimethoxysila,e (9g), methyltrimethoxy silane (31.3g), tetraethyl orthosilicate (31.1g) and PGMEA (65g) are mixed and add in the glass syringe.The 3N acetic acid (23.9g) of packing in the 3-neck round-bottomed flask of 500-mL.Unsettled agitator provides the mixing in the flask.Use syringe pump that silane/solvent blend is added in the flask in room temperature; Total interpolation time is 70 minutes.After adding silane, Dean Stark air water separator and nitrogen pipeline are connected to flask.Flask is put in the oil bath, oil bath is heated to 100 ° of C; In Dean Stark air water separator, collect distillment.After collection distillment 60 minutes, PGMEA (40g) is slowly added in the flask.Oil bath is heated to 125 ° of C, still collects distillment simultaneously, and continue other 70 minutes of heating.Collect the altogether distillment of 57.8g.Flask is removed from thermal source, remove Dean Stark air water separator.Weight-average molecular weight is defined as 2590 g/mols by GPC.Flask is put back in the oil bath of 125 ° of C.After 125 ° of C 30 minutes, take out sample from flask, weight-average molecular weight is defined as approximately 3790 g/mols by GPC.Continue other 30 minutes of heating at 125 ° of C.Flask is removed from oil bath.Weight-average molecular weight is defined as 5040 g/mols by GPC.The concentration of gained siloxane polymer solution is 23.46wt%, based on the weight of solution.
Vinyltrimethoxy silane (11.1g), phenyltrimethoxysila,e (9g), methyltrimethoxy silane (27.9g), tetraethyl orthosilicate (36.4g) and PGMEA (65g) are mixed and add in the glass syringe.The 3N acetic acid (24.1g) of packing in the 3-neck round-bottomed flask of 500-mL.Unsettled agitator provides the mixing in the flask.Use syringe pump that silane/solvent blend is added in the flask in room temperature; Total interpolation time is 60 minutes.After adding silane, Dean Stark air water separator and nitrogen pipeline are connected to flask.Flask is put in the oil bath that is heated to 100 ° of C, in Dean Stark air water separator, collected distillment 60 minutes.Then PGMEA (40g) is slowly added in the flask.Oil bath is heated to 125 ° of C, still collects distillment simultaneously, and continue other 60 minutes of heating.Collect altogether 55.1g distillment.Flask is removed from thermal source, and remove Dean Stark air water separator.Weight-average molecular weight is defined as 3770 g/mols by GPC.Flask is put back in the oil bath of 125 ° of C.After 125 ° of C 15 minutes, flask is removed and cooled off from oil bath.Weight-average molecular weight is defined as approximately 4505 g/mols by GPC.Flask is put back in the oil bath of 125 ° of C; And continue to heat other 16 minutes.Flask is removed from oil bath.Weight-average molecular weight is defined as 5620 g/mols by GPC.The concentration of gained siloxane polymer solution is 27.29wt%, based on the weight of solution.
Vinyltrimethoxy silane (11.1g), phenyltrimethoxysila,e (9g), methyltrimethoxy silane (24.5g), 41.6g tetraethyl orthosilicate (41.6g) and PGMEA (65g) are mixed and add in the glass syringe.The 3N acetic acid (24.3g) of packing in the 3-neck round-bottomed flask of 500-mL.Unsettled agitator provides the mixing in the flask.Use syringe pump that silane/solvent blend is added in the flask in room temperature; Total interpolation time is 62 minutes.After adding silane, Dean Stark air water separator and nitrogen pipeline are connected to flask.Flask is put in the oil bath that is heated to 100 ° of C; In Dean Stark air water separator, collect distillment.After collection distillment 51 minutes, PGMEA (50g) is slowly added in the flask.Oil bath is heated to 125 ° of C, still collected distillment other 45 minutes simultaneously.Collect altogether 52.5g distillment.Flask is removed from thermal source, and remove Dean Stark air water separator.Weight-average molecular weight is defined as 3020 g/mols by GPC.Flask is put back in the oil bath of 125 ° of C.After 125 ° of C 16 minutes, its cooling is removed and made to flask from oil bath.Weight-average molecular weight is defined as approximately 3675 g/mols by GPC.Flask is put back in the oil bath of 125 ° of C; Continue other 30 minutes of heating.Flask is removed from oil bath.Weight-average molecular weight is defined as 4960 g/mols by GPC.Flask is put back in the oil bath of 125 ° of C; Continue other 15 minutes of heating.Flask is removed from oil bath.Weight-average molecular weight is defined as 5925 g/mols by GPC.The concentration of gained siloxane polymer solution is 23.01wt%.
Prepolymer A
Vinyltrimethoxy silane (65.9g), phenyltrimethoxysila,e (5.9g) and methyltrimethoxy silane (3.4g) are mixed and add in the glass syringe.The 3N acetic acid (27g) of packing in the 3-neck round-bottomed flask of 500-mL.Unsettled agitator provides the mixing in the flask.Use syringe pump that silane is added in the flask; Total interpolation time is 45 minutes.After adding silane, Dean Stark air water separator and nitrogen pipeline are connected to flask.Flask is put in the oil bath that is heated to 100 ° of C.In Dean Stark air water separator, collect after the distillment 45 minutes, PGMEA (75g) is slowly added in the flask.Oil bath is heated to 125 ° of C, collected simultaneously distillment other 75 minutes.Collect altogether 49.4g distillment.Dean Stark air water separator is removed from flask.Oil bath kept other 95 minutes at 125 ° of C; Flask is removed and stopped heating from oil bath.Flask is put back in the oil bath of 125 ° of C other 60 minutes.Flask is removed from oil bath, and the PGMEA of 35g is added in the flask to help to promote cooling.The weight-average molecular weight of gained silsesquioxane polymer is defined as approximately 4255 g/mols by GPC.The target weight-average molecular weight is 5000 g/mols.Flask is put back in the oil bath of 125 ° of C other 61 minutes, then removes to determine molecular weight from oil bath.Weight-average molecular weight is defined as 4625 g/mols by GPC.Flask is put back in the oil bath of 125 ° of C other 61 minutes, then removes to determine molecular weight from oil bath.Weight-average molecular weight is defined as 5015 g/mols by GPC.The concentration of gained silsesquioxane polymer solution is 22.71wt%.
Prepolymer B
Vinyltrimethoxy silane (13.6g), phenyltrimethoxysila,e (3.4g), methyltrimethoxy silane (6.1g), glycidoxypropyltrimewasxysilane (10.8g) and PGMEA (80g) are mixed and add in the glass syringe.The 3N acetic acid (9.2g) of packing in the 3-neck round-bottomed flask of 250-mL.Unsettled agitator provides the mixing in the flask.Use syringe pump that silane/solvent blend is added in the flask in room temperature; Total interpolation time is 70 minutes.After adding silane, Dean Stark air water separator and nitrogen pipeline are connected to flask.Flask is put in the oil bath that is heated to 100 ° of C.In the DeanStark air water separator, collect after the distillment 43 minutes, PGMEA (40g) is slowly added in the flask.Oil bath is heated to 125 ° of C, collected simultaneously distillment other 68 minutes.Collect altogether 12.3g distillment.Flask is removed from thermal source, and remove Dean Stark air water separator.Weight-average molecular weight is defined as 645 g/mols by GPC.Flask is put back in the oil bath of 125 ° of C, after 120 minutes, takes out sample from flask, weight-average molecular weight is defined as approximately 1130 g/mols by GPC.Continue other 300 minutes of heating.Flask is removed from oil bath.Weight-average molecular weight is defined as 2050 g/mols by GPC.Flask is put back in the oil bath 420 minutes, and weight-average molecular weight is defined as 3460 g/mols by GPC after this.Flask is put back in the oil bath 420 minutes, and weight-average molecular weight is defined as 5480 g/mols by GPC after this.The concentration of gained silsesquioxane polymer solution is 14.03wt%, based on the weight of solution.
Prepolymer C
3-neck 250-mL flask equipped has temperature probe, has the unsettled agitator of constant RPM of 2 inches special teflon oars, and syringe pump adds joint.Silane monomer phenyltrimethoxysila,e (7.03g with distillation, 35.4mmol), methyltrimethoxy silane (38.12g, 279.8mmol) and tetraethyl orthosilicate (16.42g, 78.8mmol) weigh and put into Plastic Bottle, be transferred to reaction flask, and dilute with the PGMEA of 65.5mL.Hydrochloric acid (0.1N, 3.95mL, 3.95mmol) mixes in graduated cylinder with HPLC-grade water (19.49mL, 1082mmol) dilution, dropwise adds in the solution of silane in ambient room temperature by syringe pump in then during 30 minutes.After acid/aqueous solution interpolation step was finished, syringe pump added joint and substitutes with the short-path distillation head that is equipped with nitrogen pipeline, after this, then is adjusted to the oil bath heated solution of 110 ° of C by setting point.After 15 minutes, the oil bath temperature setting point is down to 100 ° of C.Frequently shift out reaction equal portions (0.2mL), be diluted among the THF (1.0mL) to pass through gpc analysis.After heating 75 minutes, polymers soln reaches the molecular weight close to target (5000 g/mols).With other PGMEA (46.8mL, 342mmol) with solution dilution to the 21.9wt% solid, based on the gross weight of solution, and be cooled to room temperature.Solution is stirred by the DOWEXMARATHON MR-3 mixture iron exchange resin that Dow Chemical Co. produces at excessive equivalent, and it is filtered by " 0.2 μ m " PTFE injection filter.Molecular weight passes through gpc measurement: 4079 g/mols of Mw; 1798 g/mols of Mn; MWD 2.27.
Prepolymer D
3-neck 250-mL flask equipped has temperature probe, has the unsettled agitator of constant RPM of 2 inches special teflon oars, and syringe pump adds joint.Silane monomer phenyltrimethoxysila,e (7.08g with distillation, 35.7mmol), methyltrimethoxy silane (32.96g, 242.0mmol) and tetraethyl orthosilicate (24.79g, 119.0mmol) weigh and put into Plastic Bottle, be transferred to reaction flask, and dilute with the PGMEA of 65.3mL.Hydrochloric acid (0.1N, 0.40mL, 0.04mmol) mixes in graduated cylinder with HPLC-grade water (23.2mL, 1287mmol) dilution, dropwise adds in the solution of silane in ambient room temperature by syringe pump in then during 30 minutes.After acid/aqueous solution interpolation step was finished, syringe pump added joint and substitutes with the short-path distillation head that is equipped with nitrogen pipeline.After 30 minutes acid interpolation time, in envrionment temperature material was mixed 60 minutes, then be adjusted to the oil bath heated solution of 100 ° of C by setting point.After 5 hours, the oil bath temperature setting point is increased to 120 ° of C.Frequently shift out reaction equal portions (0.2mL), be diluted among the THF (1.0mL) to pass through gpc analysis.After heating 6 hours, polymers soln reaches the molecular weight close to target (5000 g/mols).With other PGMEA (45.5mL) with solution dilution to the 22.4wt% solid, and be cooled to room temperature.Polymers soln stirs at excessive equivalent DOWEX MARATHON MR-3 mixture iron exchange resin.Make solution filter pass through " 0.2 μ m " PTFE injection filter, and store in refrigerator with about 15wt% solid.Molecular weight passes through gpc measurement: 7782 g/mols of Mw; 2294 g/mols of Mn; MWD 3.39.
Prepolymer E
The 3 neck round-bottomed flasks of 250mL are put in 20 ° of C water-baths.Be installed and connected in agitator, the water-jacketed condenser of air engine, the thermopair that is connected in temperature regulator and feed hopper at flask.The water (21.6g, 1.2 moles, 3N acetic acid) of acidifying is added in the flask.With vinyltrimethoxy silane (53.3g, 0.360 mole) and phenyltrimethoxysila,e (7.94g, 0.040 mole) pre-mixing, and add in the feed hopper.During 45 minutes silane is added in the reactor.After interpolation is finished, remove water-bath, heating jacket is placed under the flask.Remove feed hopper, Dean Stark air water separator is connected with nitrogen purge line.Slow heated solution in the oil bath that is set in 100 ° of C.When heating, in air water separator, collect distillment.When reaction reaches 100 ° of C, add the PGMEA of 100g.Oil bath slowly is heated to 125 ° of C, collects simultaneously other distillment.When oil bath temperature reaches 125 ° of C, remove air water separator.After 3 hours, stopped heating, the PGMEA of interpolation 75g mixes solution until it is cooled to room temperature.
Prepolymer 6 '
3-neck 250-mL flask equipped has temperature probe, has the unsettled agitator of constant RPM of 2 inches special teflon oars, and syringe pump adds joint.Silane monomer phenyltrimethoxysila,e (7.91g with distillation, 39.9mmol), methyltrimethoxy silane (18.10g, 132.9mmol), vinyltrimethoxy silane (36.74g, 247.9mmol) and tetraethyl orthosilicate (4.61g, 22.1mmol) weigh and put into Plastic Bottle, be transferred to reaction flask, and dilute with the PGMEA of 81.65mL.Glacial acetic acid (5.5mL, 94mmol) mixes in graduated cylinder with HPLC-grade water (21.9mL, 1215mmol) dilution, dropwise adds in the solution of silane in ambient room temperature by syringe pump in then during 60 minutes.After acid/aqueous solution interpolation step was finished, syringe pump added joint and substitutes with the short-path distillation head that is equipped with nitrogen pipeline.After 60 minutes acid interpolation time, in envrionment temperature material was mixed 60 minutes, then be adjusted to the oil bath heated solution of 100 ° of C by setting point.Frequently shift out reaction equal portions (0.2mL), be diluted among the THF (1.0mL) to pass through gpc analysis.After heating 9.5 hours, polymers soln reaches the molecular weight close to target (5000 g/mols).With other PGMEA (58.3mL) with solution dilution to the 21.0wt% solid, and be cooled to room temperature.Resin solution is filtered by " 0.2 μ m " PTFE injection filter, and polymers soln stores in refrigerator with about 20wt% solid.Molecular weight passes through gpc measurement: 4527 g/mols of Mw; 1793 g/mols of Mn; MWD 2.52.
Prepolymer 7 '
3-neck 500-mL flask equipped has temperature probe, has the unsettled agitator of constant RPM of 2 inches special teflon oars, and syringe pump adds joint.Silane monomer phenyltrimethoxysila,e (11.65g with distillation, 58.7mmol), methyltrimethoxy silane (44.42g, 326.0mmol), vinyltrimethoxy silane (34.85g, 234.7mmol) and tetraethyl orthosilicate (6.79g, 32.6mmol) weigh and put into Plastic Bottle, be transferred to reaction flask, and dilute with the PGMEA of 116.7mL.Glacial acetic acid (8.10mL, 138mmol) mixes in graduated cylinder with HPLC-grade water (32.3mL, 1792mmol) dilution, dropwise adds in the solution of silane in ambient room temperature by syringe pump in then during 60 minutes.After acid/aqueous solution interpolation step was finished, syringe pump added joint and substitutes with the short-path distillation head that is equipped with nitrogen pipeline.After 60 minutes acid interpolation time, in envrionment temperature material was mixed 60 minutes, then be adjusted to the oil bath heated solution of 100 ° of C by setting point.Frequently shift out reaction equal portions (0.2mL), be diluted among the THF (1.0mL) to pass through gpc analysis.After heating 10.5 hours, polymers soln reaches the molecular weight close to target (5000 g/mols).With other PGMEA (83.3mL) with solution dilution to the 22.3wt% solid, and be cooled to room temperature.Resin solution is filtered by " 0.2 μ m " PTFE injection filter, and polymers soln stores in refrigerator with about 20wt% solid.Molecular weight passes through gpc measurement; 4384 g/mols of Mw; 1722 g/mols of Mn; MWD 2.55.
Prepolymer 8 '
In the 3 neck round-bottomed flasks of the 250mL that is equipped with magnetic stirring apparatus and short-path distillation equipment, pack into phenyltrimethoxysila,e (4.86g), methyltrimethoxy silane (22.24g) and vinyltrimethoxy silane (20.57g).The solution of glacial acetic acid (5.15g) and water (23.53g) is added in the flask, and begin to stir.Then add tetraethyl orthosilicate (17.01g), with mixture stirring at room 60 minutes.Along with hydrolysis is carried out, the reaction mixture homogenizing that is separated at first, thus obtain clear soln, observe heat release.Add PGMEA (70g), and flask is put in the oil bath of controlled temperature.Oil bath is heated to 100 ° of C and kept 1 hour, then increase to 110 ° of C and kept 1 hour, then increase to 120 ° of C.When the temperature of reaction mixture reaches 100 ° of C, remove heating bath, make the polymers soln cooling.Add the PGMEA of the second equal portions, thereby polymers soln is adjusted to the 20wt% solid.The solid content of polymers soln was determined by the sample of heated polymerizable thing solution in the baking oven of 145 ° of C in 1 hour.The molecular weight of polymkeric substance is determined by GPC: Mw 2071; Mn 1268; MWD 1.63.
Prepolymer 9 '
In the 3 neck round-bottomed flasks of the 250mL that is equipped with magnetic stirring apparatus and short-path distillation equipment, pack into phenyltrimethoxysila,e (4.84g), methyltrimethoxy silane (22.24g) and vinyltrimethoxy silane (20.58g).To be added in the flask by the solution of " 0.1N HCl (0.41g) " and water (23.22g) preparation, and begin to stir.Then, add tetraethyl orthosilicate (17.02g), with mixture stirring at room 60 minutes.Along with hydrolysis is carried out, the reaction mixture homogenizing that is separated at first, thus obtain clear soln, observe heat release.Add PGMEA (50g), and flask is put in the oil bath of controlled temperature.Oil bath is heated to 100 ° of C and kept 1 hour, then increase to 110 ° of C and kept 1 hour, then increase to 120 ° of C.When the temperature of reaction mixture reaches 100 ° of C, remove heating bath, make the polymers soln cooling.Add the PGMEA of the second equal portions, thereby polymers soln is adjusted to the 20wt% solid.Residual acid is filled with AMBERLITE IRN 150 mixed-bed ion exchange resins by polymers soln is passed ion exchange column removes, and this exchange resin is produced by The Dow Chemical Company.The solid content of polymers soln was determined by the sample of heated polymerizable thing solution in the baking oven of 145 ° of C in 1 hour.The molecular weight of polymkeric substance is determined by GPC: Mw 2925; Mn 1540; MWD 1.9.
The formation of the second composition
Unless point out in addition, otherwise except the second composition 9 ', the second all compositions forms according to the universal process that the application describes.
Prepolymer (37.5g), BTEAC (0.37g) and the PGMEA (263g) of appointment are added in the Plastic Bottle, fully mix, and filter by 0.2 μ m PVDF strainer, to form each second composition.
For the second composition 9 ', prepolymer 8 (37.5g) and PGMEA (263g) are added in the Plastic Bottle, fully mix, and filter by " 0.2 μ m " PVDF strainer to form the second composition 9 '.Table 3 has been summed up all second compositions that are used for this research.
Table 3: the description of the second composition
Form (PTD) photo-resist of the positive tone development of ArF (Positive Tone Development)
Suitable positive tone development photo-resist is formed by following mixture: the 28.60g methyl proxitol acetate, 19.30g pimelinketone, 48.25g beta-hydroxymethyl butyrate, 3.02g methacrylic acid sec.-propyl-adamantane esters, methyl methacrylate base cyclopentyl ester, methacrylic acid (3aR, 4s, 5R, 7S, 7aR)-3-oxygen octahydro-4,7-epoxy group(ing)-isobenzofuran-5-base ester, the firm alkyl ester of hydroxyethyl methacrylate fund is with the multipolymer of the weight-average molecular weight of 20/20/30/20/10 mol ratio separately and 9,000, (0.46g 4-(tertiary butyl) phenyl) phenylbenzene sulfonium 1,1-two fluoro-2-(((1r, 3s, 5R, 7S)-and 3-hydroxyadamantane-1-yl) methoxyl group)-2-oxidative ethane sulfonate, 0.04g the tertiary butyl (1,3-dihydroxyl-2-(hydroxymethyl)-propane-2-yl) carbamate, and the surperficial levelling agent fluoridized of 0.01g PolyFox 656.
Form (NTD) photo-resist of the negative tone development of ArF (Negative Tone Development)
Suitable negative tone development photo-resist is formed by following mixture: the 28.95g methyl proxitol acetate; 19.30g pimelinketone; 48.25g beta-hydroxymethyl butyrate; 2.89g methacrylic acid (2; 2-dimethyl-1; 3-dioxolane-4-yl) methyl ester; methacrylic acid 5-(2; 2-dimethyl-1; 3-dioxolane-4-yl)-2; 2-dimethyl-tetrahydrofuran base [2; 3-d] [1; 3] dioxolane-(5-(2 for 6-base ester; 2-dimethyl-1; 3-dioxolan-4-yl)-2; 2-dimethyltetrahydrofuro[2; 3-d] [1; 3] dioxol-6-yl methacrylate); the firm alkyl ester of methyl methacrylate fund/methacrylic acid 5-oxo-4-oxa--three ring ninth of the ten Heavenly Stems-2-base oxygen carbonyl methyl ester; vinylformic acid hydroxyadamantane base ester is with 25/25/40/10 mol ratio and 22 separately; the multipolymer of 000 weight-average molecular weight; 0.49g triphenyl-sulfonium-1; 1; 2; 2-tetrafluoro-4-((4-(13-methyl-3; 7; 12-trioxy-16 hydrogen-1H-encircles penta [a] phenanthrene-17-yl) pentanoyl) oxygen) butane-1-sulfonate, the 0.07g weight-average molecular weight is the polymkeric substance of 10,000 n-BMA; 0.05g dodecyl diethanolamine, and the surperficial levelling agent fluoridized of 0.01g PolyFox 656.
The formation of single-layer coating
In clean room environment (approximately 72 °F, about 50%RH, grade 100), derive from unprimed " 200mm " diameter silicon wafer of WaferNet Inc. as substrate.On the Si wafer, manually scatter the second composition, apply the nominal film thickness degree (at THERMA-WAVE spectrum ellipsometer record) of spin coating to reach 35nm on the track at Tokyo Electron (TEL) ACT-8.The wafer of coating was 240 ° of C bakings 60 seconds.Single-layer coating is summarized in table 4A, 4B and 4C.
Table 4A: the description of single-layer coating
Table 4B: the description of single-layer coating is continuous
Table 4C: the description of single-layer coating is continuous
| Individual layer A | Individual layer B | Individual layer C | Individual layer D |
| The second composition C | The second composition D | The second composition A | The second composition E |
Testing method on the single-layer coating
Measure optical property (n, k is at 193nm) and film thickness
The optical property of film and thickness use WOOLAM VUV-VASE VU-302 ellipsometer (Woolam, NE) to measure.Film is coated with at the naked silicon wafer of " 200mm " diameter, as described in above single-layer coating part.Polarization data is collected three angles in the wavelength region of 170nm to 900nm.Data produce automatically, thereby obtain the thickness of film and in the specific refractory power (n, k) of 193nm, wherein n is the real component of complex index, and k is the imaginary component of complex index.
Table 5 has been summed up the embodiment of the invention and Comparative Examples at the refractive index n of 193nm, k.Reflection minimize optical constant and the thickness that depends on anti-reflection layer.When using the desired thickness of 20nm to 50nm, computer uses PROLITH software V10.0 (KLA-Tencor Corporation) to simulate, show at 193nm, n be not less than 1.67 and k be 0.15 to 0.3, reflex to less than 0.5% thereby reduce.As shown in table 5, the n value of all embodiment of the invention and k value within the required range, two Comparative Examples n value separately all is lower than required.Therefore the embodiment of the invention be good anti-reflection layer therefore, and Comparative Examples is relatively poor aspect this providing good performance aspect the control reflection.
Table 5: the optical property of the embodiment of the invention and Comparative Examples
| n | k | ||
| The present invention | The present invention | ||
| Embodiment 1 | Individual layer 1 | 1.67 | 0.21 |
| Embodiment 2 | Individual layer 2 | 1.68 | 0.22 |
| Embodiment 3 | Individual layer 3 | 1.69 | 0.23 |
| Embodiment 4 | Individual layer 4 | 1.68 | 0.22 |
| |
|
1.68 | 0.22 |
| |
|
1.67 | 0.21 |
| |
|
1.67 | 0.20 |
| |
|
1.67 | 0.20 |
| Contrast | Contrast | ||
| The comparative example A | Individual layer A | 1.65 | 0.19 |
| Comparative Examples B | Individual layer B | 1.66 | 0.19 |
Measure water contact angle
As above discuss, single-layer coating is at 1 hour inner analysis of coating.DATAPHYSICS Instruments GmbH, model OCA20 protractor are used for all contact angles and measure.Deionized water is as test liquid.1 microlitre drop is used for each time contact angle and measures.After drop is dispersed on the surface of single-layer coating, measures for each time and to use the protractor camera to record minimum 10 seconds liquid drop movement with the minimum-rate of 3 frame/seconds.When the protractor pin fully when removing within sweep of the eye and do not have liquid drop movement, first drop image is used for determining contact angle.Contact angle uses the doughnut model (circular model) in the OCA software to estimate.Minimumly on whole single-layer coating carry out three independent measurements (three every single-layer coatings of drop).The typical standard deviation that contact angle is measured is about 0.2 degree.
Table 6 has been summed up the water contact angle result of the embodiment of the invention and Comparative Examples.For obtain good pattern in the photoengraving technological process, film quality is crucial.Layer of the present invention probably is used for the multilayer scheme, wherein will be coated with another layer at the top of layer of the present invention.If the surface energy of layer of the present invention excessively low (by high water contact angle indication), defective for example dehumidification (dewets) (this occurs when film does not cover dispensing area fully) may occur in the rete above the layer of the present invention.For the surface imperfection that makes adjacent layer minimizes, the water contact angle of layer of the present invention is preferably less than 87 °.As shown in table 6, the water contact angle of all embodiment of the invention is less than the contact angle of Comparative Examples, and the contact angle of embodiment of the invention 1-8 is less than 87 °.Under the contrast, the water contact angle of Comparative Examples C and D is respectively 90 °, 93 °.
Table 6: the water contact angle of the embodiment of the invention and Comparative Examples
| The present invention | The present invention | Water CA |
| Embodiment 1 | Individual layer 1 | 80 |
| Embodiment 2 | Individual layer 2 | 79 |
| Embodiment 3 | Individual layer 3 | 70 |
| Embodiment 4 | Individual layer 4 | 79 |
| |
|
77 |
| |
|
83 |
| |
|
77 |
| |
|
75 |
| Embodiment 9 ' | Individual layer 9 ' | 87.5 |
| Embodiment 10 ' | Individual layer 10 ' | 88.6 |
| Contrast | Contrast | Water CA |
| Comparative Examples C | Individual layer C | 90 |
| Comparative Examples D | Individual layer D | 93 |
Form duplex coating
Film according to form the single-layer coating part be coated with describing.Then be applied over ArF PTD photo-resist on the wafer of coating by spin coating, wafer appropriateness baking (soft-baked) 100 ° of C of coating are reached 60 seconds, thereby obtain the photo-resist film thickness (recording at Therma-Wave spectrum ellipsometer) of 100nm.Double-deck summary is provided in table 7.
Table 7: double-deck description
Estimate the binding property of duplex coating
After duplex coating forms, carry out the binding property test.The band according to the ASTMD3359 tractive is used in the binding property test.At first, be with (3M, MN) securely by being pressed on the ArF PTD photo-resist coating Scotch.The length of stick portion is 1 inch, and the free section that residue connects is divided at least 1 inch.Pull back fast with angle coatingsurface with the freely part of two banjo splint taut bands and with approximately 270 °.After traction belt, the remaining coating of visual inspection, the area that is transferred to band on the coating is evaluated as the long-pending per-cent of belt surface that is bonded to coating.The good binding property of " 0% peels off " expression, and " 100% peels off " expression binding property lost efficacy.To test and repeat at least five times, report the per-cent of the area of bonding coating, as shown in table 8.
The photolithographic three layers of coating of pattern need to have good interlaminar adhesion.If a little less than the binding property, layering may occur in photoetching process, perhaps destroy when pattern may occur during less than dissimilar power (for example excess force, thermal stresses, solvent-swollen stress and capillary force) bounding force.Table 8 shows, all embodiment of the invention all have good binding property, and Comparative Examples has poor interlaminar adhesion.
Table 8: the binding property measuring result of the embodiment of the invention and Comparative Examples
| Dry adhesion | ||
| Embodiment 13 | Double-deck 1 | 0% peels off |
| Embodiment 14 | Double-deck 2 | 0% peels off |
| Embodiment 15 | Double-deck 3 | 0% peels off |
| Embodiment 16 | Double-deck 4 | 0% peels off |
| Embodiment 17 | Double- |
0% peels off |
| Embodiment 18 | Double- |
0% peels off |
| Embodiment 19 | Double- |
0% peels off |
| Embodiment 20 | Double- |
0% peels off |
| Comparative Examples E | Three layers of A | 100% peels off |
| Comparative Examples F | Three layers of B | 100% peels off |
Form three layers of coating
Layer of the present invention is used for three layered schemes with the check lithography performance.Three layers general structure as shown in Figure 1.
Form bottom
To be applied over available from WaferNet based on the primer coating composition of organic poly-(methacrylic ester) by spin coating, the silicon wafer of " 300mm " diameter of Inc. toasts the wafer that is coated with 60 seconds at 240 ° of C, to realize the film thickness of 135nm.Suitable primer coating composition comprises AR26N, available from Dow Chemical Company.
Form layer of the present invention at bottom
By spin coating the coating composition of the present invention of describing in the table 9 is applied over wafer from the prime-coating of previous step.Each coating was toasted 60 seconds at 240 ° of C, to realize the film thickness of the present invention of 35nm.
Form three layers
ArF photo-resist (PTD and NTD are as described before) is applied over the wafer (from previous step) of coating by spin coating, the wafer that is coated with was toasted 60 seconds 100 ° of C appropriateness, to realize the photo-resist coated membrane thickness of 100nm.Topcoating can be applied over the leaching control that PTD photo-resist coating needs so that " 193nm " immersion lithography machining to be provided.Suitable Topcoating comprises OC2000, derives from Dow Chemical Company.
Table 9: the description of three layers of coating
| Three layer 1 | Three layer 2 | Three layer 3 | Three layer 4 | Three layers of A | Three layers of B |
| The second composition 1 | The |
The |
The second composition 3 | The second composition B | The second composition B |
Form photoengraving pattern
Lithography process
Three layers of coating that form are processed according to following steps:
1) exposure: use ASML 1900i, make the layer of the photo-resist that applies be exposed to the 193nm radiation that forms pattern;
2) postexposure bake: 120 ° of C carried out 60 seconds;
3) develop: latent image-use 0.26N alkali aqueous solution photographic developer develops to obtain positive photo-resist camegraph, or develop to obtain the negative photoresist camegraph with suitable organic solvent (for example OSD-1000 organic solvent photographic developer derives from Dow Chemical Company).
Estimate the lithography performance of three layers of coating
Fig. 2 has described the schematic diagram of two kinds of photo-resist line cross sections.Required photo-resist line cross section is shown in Fig. 2 a.Cross section shows square profiles.The cross-sectional profile of not expecting is shown in Fig. 2 b.The CD (critical size) that the cross section of not expecting shows in feature bottom increases.This appearance defect is commonly referred to footprint or scum silica frost.
Another aspect of photo-resist performance is " pattern breaking limit ".Expectation can obtain the pattern of minimum between-line spacing, prevents simultaneously or reduce " slump (fall over) " or the destruction of the pattern of so little between-line spacing.Do not provide the suitable fusible hard mask compositions to photo-resist may cause pattern to destroy, shown in the top-down SEM image among Fig. 3.Fig. 4 illustrates the quantitative definition of pattern breaking limit.Numeral among this figure is the width of groove in " 140nm pitch pattern ".The pattern breaking limit is higher, and the width of vertical curve (standing lines) is just narrower, and therefore lithography performance is better aspect the minimum size that can form.
After photolithography, high expectations obtains, and do not have the photo-resist pattern of scum silica frost, and this pattern has high pattern breaking limit.Table 10 has compared the profile degree of cleaning (lacking scum silica frost) of the embodiment of the invention and Comparative Examples.Fig. 5 shows, the embodiment of the invention 16 has the square profiles that does not contain scum silica frost, and observes scum silica frost in the profile of Comparative Examples G, as shown in Figure 6.Table 11 has compared the pattern breaking limit of the embodiment of the invention and Comparative Examples.As the table shows, the embodiment of the invention has good pattern breaking limit, and Comparative Examples has complete pattern destruction.
Table 10: the photoengraving pattern performance of the embodiment of the invention and Comparative Examples
| Embodiment | Three layers | Visualization mode | Scum silica frost | Image |
| Embodiment 21 | Three layer 1 | Positive development | Nothing | Fig. 5 |
| Embodiment 22 | Three layer 2 | Positive development | Nothing | |
| Comparative Examples G | Three layers of A | Positive development | Have | Fig. 6 |
Table 11: the photoengraving pattern performance of the embodiment of the invention and Comparative Examples
| Visualization mode | Scum silica frost | Pattern breaking limit (nm) | ||
| The present invention | The present invention | |||
| Embodiment 23 | Three layer 3 | Negative development | Nothing | 85 |
| Embodiment 24 | Three layer 4 | Negative development | Nothing | 95 |
| Contrast | Contrast | |||
| Comparative Examples H | Three layers of B | Negative development | Pattern destroys fully |
Claims (15)
1. the first composition comprises following at least component:
A) be selected from the compound F 17-hydroxy-corticosterone 1 of formula 1:
Wherein Ra comprises one or more multiple bonds, and condition is, if Ra comprise more than a multiple bond, these multiple bonds are not the configuration of conjugation so; With
R1, R2 and R3 are selected from alkoxyl group, hydroxyl, halogen, OC (O) R or OC (O) OR independently of one another, and wherein R is the alkyl of alkyl or replacement; With
B) be selected from the compound F 17-hydroxy-corticosterone 2 of formula 2
Wherein Rb is selected from H or saturated group, and described saturated group comprises alkyl, alkylene or alkylidene; R4, R5 and R6 are selected from alkoxyl group, hydroxyl, halogen, OC (O) R or OC (O) OR independently of one another, and wherein R is the alkyl of alkyl or replacement; With
C) be selected from the compound F 17-hydroxy-corticosterone 3 of formula 3:
Wherein Rc comprises more than a multiple bond, and these multiple bonds are the configuration of conjugation; R7, R8 and R9 are selected from alkoxyl group, hydroxyl, halogen, OC (O) R or OC (O) OR independently of one another, and wherein R is the alkyl of alkyl or replacement; With
D) be selected from the compound F 17-hydroxy-corticosterone 4 of formula 4:
Wherein R10, R11, R12 and R13 are selected from alkoxyl group, hydroxyl, halogen, OC (O) R or OC (O) OR independently of one another, and wherein R is the alkyl of alkyl or replacement.
2. the first composition of claim 1 comprises the Si more than or equal to 5wt%, based on the gross weight of compound F 17-hydroxy-corticosterone 1, F2, F3 and F4.
3. the first composition of claim 1 or claim 2, wherein the integral molar quantity of compound F 17-hydroxy-corticosterone 2 and compound F 17-hydroxy-corticosterone 4 is more than or equal to 40 % by mole, based on the total mole number of compound F 17-hydroxy-corticosterone 1, F2, F3 and F4.
4. each the first composition in the aforementioned claim, wherein the amount of compound F 17-hydroxy-corticosterone 4 is greater than 10 % by mole, based on the total mole number of compound F 17-hydroxy-corticosterone 1, F2, F3 and F4.
5. each the first composition in the aforementioned claim, wherein the amount of compound F 17-hydroxy-corticosterone 1 is greater than 10 % by mole, based on the total mole number of compound F 17-hydroxy-corticosterone 1, F2, F3 and F4.
6. each the first composition in the aforementioned claim, wherein the amount of compound F 17-hydroxy-corticosterone 4 is less than 65 % by mole, based on the total mole number of compound F 17-hydroxy-corticosterone 1, F2, F3 and F4.
7. the prepolymer that is formed by each the first composition in the aforementioned claim.
8. the second composition, it comprises the prepolymer of claim 7; At least a with in the following material: contain the compound of amine, halogen-containing compound, hydrochloride contains the compound of ammonium or its mixture.
9. the crosslinked composition that is formed by the second composition of claim 8.
10. the goods that comprise at least one parts that formed by each composition in the aforementioned claim.
11. comprise at least one by each composition among the claim 1-9 form the layer film.
12. the film of claim 11 also comprises the second layer that is formed by the 3rd composition that comprises polymkeric substance.
13. form the method for coating in substrate, described method comprises at least following steps:
Substrate is provided,
Form bottom in described substrate, wherein said bottom comprises at least a polymkeric substance,
Each the first composition or the second composition of claim 8 among the claim 1-6 are applied on the described bottom, and
Make the first composition or the second composition solidify to form described coating.
14. the method for claim 13, wherein a plurality of layers with the first composition or the second composition are applied on the described bottom.
15. the method for claim 13 or claim 14, wherein said coating is anti-reflection layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161537098P | 2011-09-21 | 2011-09-21 | |
| US61/537,098 | 2011-09-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103031059A true CN103031059A (en) | 2013-04-10 |
| CN103031059B CN103031059B (en) | 2017-09-26 |
Family
ID=47018789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210355169.XA Active CN103031059B (en) | 2011-09-21 | 2012-09-21 | Composition and anti-reflection coating for photoetch method |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US9011591B2 (en) |
| EP (1) | EP2597518B1 (en) |
| JP (1) | JP6006594B2 (en) |
| KR (1) | KR102066468B1 (en) |
| CN (1) | CN103031059B (en) |
| TW (1) | TWI641912B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9366964B2 (en) | 2011-09-21 | 2016-06-14 | Dow Global Technologies Llc | Compositions and antireflective coatings for photolithography |
| TWI582180B (en) * | 2011-12-21 | 2017-05-11 | 陶氏全球科技有限責任公司 | Compositions for antireflective coatings |
| US9068086B2 (en) | 2011-12-21 | 2015-06-30 | Dow Global Technologies Llc | Compositions for antireflective coatings |
| JP2014202969A (en) * | 2013-04-05 | 2014-10-27 | 富士フイルム株式会社 | Pattern forming method, electronic device and method for manufacturing the same |
| US9123656B1 (en) | 2014-05-13 | 2015-09-01 | Taiwan Semiconductor Manufacturing Co., Ltd. | Organosilicate polymer mandrel for self-aligned double patterning process |
| EP3194502A4 (en) * | 2015-04-13 | 2018-05-16 | Honeywell International Inc. | Polysiloxane formulations and coatings for optoelectronic applications |
| CN107533302B (en) * | 2015-05-25 | 2022-02-01 | 日产化学工业株式会社 | Composition for coating resist pattern |
| US9442377B1 (en) | 2015-06-15 | 2016-09-13 | Rohm And Haas Electronic Materials Llc | Wet-strippable silicon-containing antireflectant |
| JP2017097240A (en) * | 2015-11-26 | 2017-06-01 | Jsr株式会社 | Material for forming silicon-containing film and pattern formation method |
| KR102581806B1 (en) | 2020-12-30 | 2023-09-25 | 세메스 주식회사 | Apparatus for treating substrate and method for treating substrate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101523292A (en) * | 2006-10-12 | 2009-09-02 | 日产化学工业株式会社 | Method for manufacturing semiconductor device using quadruple-layer laminate |
| US20100087233A1 (en) * | 2008-06-10 | 2010-04-08 | Samsung Electronics Co., Ltd. | Extendable sliding module and mobile terminal having the same |
| WO2010087233A1 (en) * | 2009-01-28 | 2010-08-05 | Jsr株式会社 | Silicon-containing film, resin composition, and pattern formation method |
Family Cites Families (42)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4442197A (en) | 1982-01-11 | 1984-04-10 | General Electric Company | Photocurable compositions |
| FR2525846A1 (en) | 1982-04-22 | 1983-10-28 | Boga Sa | METHOD AND APPARATUS FOR SELECTING CONNECTION POINTS FROM A TELEPHONE DISTRIBUTOR |
| EP0100891A1 (en) | 1982-08-17 | 1984-02-22 | Contraves Ag | Method and apparatus for providing coincidence correction during the counting of two kinds of particles |
| EP0153904B1 (en) | 1984-02-10 | 1988-09-14 | Ciba-Geigy Ag | Process for the preparation of a protection layer or a relief pattern |
| DK241885A (en) | 1984-06-01 | 1985-12-02 | Rohm & Haas | PHOTOSENSIBLE COATING COMPOSITIONS, THERMALLY STABLE COATINGS MADE THEREOF AND APPLICATION OF SUCH COATINGS FOR THE formation of THERMALLY STABLE POLYMER PICTURES |
| US5128232A (en) | 1989-05-22 | 1992-07-07 | Shiply Company Inc. | Photoresist composition with copolymer binder having a major proportion of phenolic units and a minor proportion of non-aromatic cyclic alcoholic units |
| US5100503A (en) | 1990-09-14 | 1992-03-31 | Ncr Corporation | Silica-based anti-reflective planarizing layer |
| DE69322946T2 (en) | 1992-11-03 | 1999-08-12 | International Business Machines Corp., Armonk, N.Y. | Photoresist composition |
| US5344742A (en) | 1993-04-21 | 1994-09-06 | Shipley Company Inc. | Benzyl-substituted photoactive compounds and photoresist compositions comprising same |
| DE19515540A1 (en) | 1995-04-27 | 1996-10-31 | Wacker Chemie Gmbh | Stabilization of reactive organopolysiloxane resins |
| US5843624A (en) | 1996-03-08 | 1998-12-01 | Lucent Technologies Inc. | Energy-sensitive resist material and a process for device fabrication using an energy-sensitive resist material |
| US5861231A (en) | 1996-06-11 | 1999-01-19 | Shipley Company, L.L.C. | Copolymers and photoresist compositions comprising copolymer resin binder component |
| US6090526A (en) | 1996-09-13 | 2000-07-18 | Shipley Company, L.L.C. | Polymers and photoresist compositions |
| KR100220951B1 (en) | 1996-12-20 | 1999-09-15 | 김영환 | Vinyl 4-tetrahydropyraniloxybenzal-vinyl 4-hydroxybenzal-vinyltetrahydropyranil ether-vinyl acetate copolymer |
| US6057083A (en) | 1997-11-04 | 2000-05-02 | Shipley Company, L.L.C. | Polymers and photoresist compositions |
| JP4327360B2 (en) | 1998-09-23 | 2009-09-09 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Photoresist, polymer and microlithography methods |
| KR20000047909A (en) | 1998-12-10 | 2000-07-25 | 마티네즈 길러모 | Itaconic anhydride polymers and photoresist compositions comprising same |
| US6048662A (en) | 1998-12-15 | 2000-04-11 | Bruhnke; John D. | Antireflective coatings comprising poly(oxyalkylene) colorants |
| US6048664A (en) | 1999-03-12 | 2000-04-11 | Lucent Technologies, Inc. | Energy-sensitive resist material and a process for device fabrication using an energy-sensitive resist material |
| US6268457B1 (en) | 1999-06-10 | 2001-07-31 | Allied Signal, Inc. | Spin-on glass anti-reflective coatings for photolithography |
| CA2401572A1 (en) * | 2000-02-28 | 2001-09-07 | Adsil, Lc | Silane-based, coating compositions, coated articles obtained therefrom and methods of using same |
| US6306554B1 (en) | 2000-05-09 | 2001-10-23 | Shipley Company, L.L.C. | Polymers containing oxygen and sulfur alicyclic units and photoresist compositions comprising same |
| TW200505966A (en) | 2003-04-02 | 2005-02-16 | Dow Global Technologies Inc | Organosilicate resin formulation for use in microelectronic devices |
| US7303785B2 (en) | 2003-06-03 | 2007-12-04 | Shin-Etsu Chemical Co., Ltd. | Antireflective film material, and antireflective film and pattern formation method using the same |
| US7223517B2 (en) | 2003-08-05 | 2007-05-29 | International Business Machines Corporation | Lithographic antireflective hardmask compositions and uses thereof |
| JP4553113B2 (en) | 2004-06-10 | 2010-09-29 | 信越化学工業株式会社 | Porous film-forming composition, pattern-forming method, and porous sacrificial film |
| JP4491283B2 (en) | 2004-06-10 | 2010-06-30 | 信越化学工業株式会社 | Pattern formation method using antireflection film-forming composition |
| JP4638380B2 (en) * | 2006-01-27 | 2011-02-23 | 信越化学工業株式会社 | Antireflection film material, substrate having antireflection film, and pattern forming method |
| US20070212886A1 (en) * | 2006-03-13 | 2007-09-13 | Dong Seon Uh | Organosilane polymers, hardmask compositions including the same and methods of producing semiconductor devices using organosilane hardmask compositions |
| JP5112733B2 (en) | 2006-04-11 | 2013-01-09 | ローム・アンド・ハース・エレクトロニック・マテリアルズ，エル．エル．シー． | Coating composition for photolithography |
| US7736837B2 (en) | 2007-02-20 | 2010-06-15 | Az Electronic Materials Usa Corp. | Antireflective coating composition based on silicon polymer |
| US8026040B2 (en) * | 2007-02-20 | 2011-09-27 | Az Electronic Materials Usa Corp. | Silicone coating composition |
| TWI434891B (en) * | 2007-02-22 | 2014-04-21 | Silecs Oy | High silicon content siloxane polymers for integrated circuits |
| US20100210765A1 (en) | 2007-10-01 | 2010-08-19 | Nissan Chemical Industries, Ltd. | Resist underlayer film-forming composition, production method of semiconductor device using the same, and additive for resist underlayer film-forming composition |
| JP2009199061A (en) | 2007-11-12 | 2009-09-03 | Rohm & Haas Electronic Materials Llc | Coating compositions for use with overcoated photoresist |
| WO2009069712A1 (en) * | 2007-11-30 | 2009-06-04 | Nissan Chemical Industries, Ltd. | Blocked isocyanato bearing silicon containing composition for the formation of resist undercoat |
| JP5587791B2 (en) | 2008-01-08 | 2014-09-10 | 東レ・ダウコーニング株式会社 | Silsesquioxane resin |
| JP5365809B2 (en) * | 2008-02-18 | 2013-12-11 | 日産化学工業株式会社 | Silicon-containing resist underlayer film forming composition having cyclic amino group |
| JP5015891B2 (en) | 2008-10-02 | 2012-08-29 | 信越化学工業株式会社 | Metal oxide-containing film forming composition, metal oxide-containing film forming substrate, and pattern forming method |
| EP2372458A4 (en) * | 2008-12-19 | 2012-06-06 | Nissan Chemical Ind Ltd | Silicon-containing resist underlayer film formation composition having anion group |
| JP4941684B2 (en) * | 2009-03-27 | 2012-05-30 | 信越化学工業株式会社 | Photomask blank and processing method thereof |
| JP5534250B2 (en) * | 2009-09-16 | 2014-06-25 | 日産化学工業株式会社 | Silicon-containing resist underlayer film forming composition having sulfonamide group |
-
2012
- 2012-08-28 US US13/596,191 patent/US9011591B2/en active Active
- 2012-09-18 EP EP12184808.9A patent/EP2597518B1/en not_active Not-in-force
- 2012-09-20 KR KR1020120104391A patent/KR102066468B1/en active IP Right Grant
- 2012-09-20 JP JP2012207144A patent/JP6006594B2/en not_active Expired - Fee Related
- 2012-09-20 TW TW101134483A patent/TWI641912B/en not_active IP Right Cessation
- 2012-09-21 CN CN201210355169.XA patent/CN103031059B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101523292A (en) * | 2006-10-12 | 2009-09-02 | 日产化学工业株式会社 | Method for manufacturing semiconductor device using quadruple-layer laminate |
| US20100087233A1 (en) * | 2008-06-10 | 2010-04-08 | Samsung Electronics Co., Ltd. | Extendable sliding module and mobile terminal having the same |
| WO2010087233A1 (en) * | 2009-01-28 | 2010-08-05 | Jsr株式会社 | Silicon-containing film, resin composition, and pattern formation method |
Also Published As
| Publication number | Publication date |
|---|---|
| US20130071560A1 (en) | 2013-03-21 |
| CN103031059B (en) | 2017-09-26 |
| EP2597518A2 (en) | 2013-05-29 |
| TW201317716A (en) | 2013-05-01 |
| KR102066468B1 (en) | 2020-01-16 |
| JP2013067798A (en) | 2013-04-18 |
| US9011591B2 (en) | 2015-04-21 |
| EP2597518A3 (en) | 2015-07-01 |
| TWI641912B (en) | 2018-11-21 |
| EP2597518B1 (en) | 2016-12-07 |
| KR20130031798A (en) | 2013-03-29 |
| JP6006594B2 (en) | 2016-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103031059A (en) | Compositions and antireflective coatings for photolithography | |
| KR101339763B1 (en) | Antireflective hard mask compositions | |
| JP5093352B2 (en) | Negative photosensitive composition, optical element partition using the same, and optical element having the partition | |
| JP5803938B2 (en) | Negative photosensitive resin composition, partition for optical element and method for producing the same, and method for producing optical element having the partition | |
| US9817312B2 (en) | Silicon-containing heat- or photo-curable composition | |
| JP6424832B2 (en) | Negative photosensitive resin composition, cured resin film, partition wall and optical element | |
| CN101617011A (en) | Antireflective coating compositions based on silicon polymer | |
| KR20180120784A (en) | Photosensitive siloxane composition | |
| KR20180136942A (en) | Resin composition, a cured film thereof, a production method thereof, and a solid- | |
| TWI588610B (en) | Photo-patternable and developable silsesquioxane resins for use in device fabrication | |
| CN103113827B (en) | Compositionss for photo-engraving process and anti-reflection coating | |
| TW201934618A (en) | Photosensitive siloxane composition and pattern forming method using the same | |
| CN113631672B (en) | Positive photosensitive polysiloxane composition | |
| KR102013960B1 (en) | Compositions for antireflective coatings | |
| JP2021155467A (en) | Resin, photosensitive resin composition, cured material, organic el display device, semiconductor device and manufacturing method of cured material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |